KR101665757B1 - Shaped silica body, process for producing same, and method for manufacturing propylene using shaped silica body - Google Patents

Abstract

The present invention provides a silica molded body which is less prone to dealumination of zeolite even in a high temperature water vapor atmosphere and is less susceptible to corrosion of stainless steel commonly used in industrial equipment, a process for producing the same, and a process for producing propylene using the silica formed product Purpose and problem. The method for producing a silica compact according to the present invention comprises the steps of preparing a raw material mixture containing silica and zeolite, obtaining a dried body by drying the raw material mixture, and calcining the dried body, Or phosphoric acid and / or phosphate solution is brought into contact with the zeolite and / or the dried body, or a combination thereof, the content of the phosphorus element in the silica-formed body is larger than the mass of the entire silica- To 0.01% by mass to 1.0% by mass with respect to the total mass of the catalyst.

Description

TECHNICAL FIELD [0001] The present invention relates to a silica molded article, a method for producing the same, and a method for producing propylene using a silica formed article,

The present invention relates to a silica shaped article containing phosphorus elements, a method for producing the same, and a method for producing propylene using the silica shaped article.

Lower olefins such as ethylene, propylene and butene are important raw materials in the chemical industry. In particular, propylene has been expected to grow in recent years, and various types of manufacturing methods have been actively developed and improved. Propylene is mainly produced by pyrolysis of naphtha or catalytic cracking of petroleum heavy fractions using a catalyst. The reaction system is mainly a fluidized bed reaction, and USY type zeolite or MFI type zeolite is used as a catalyst . In these catalysts, a heavy carbonaceous material (coke) accumulates in the zeolite pores due to reaction with hydrocarbons, and the catalyst may be inactivated. Therefore, it is necessary to regenerate the catalyst by burning off the coke in an atmosphere containing oxygen. However, there is a problem that the aluminum in the crystal lattice, which is the active point of the zeolite, escapes from the crystal lattice due to the water generated in association with the combustion of the coke, thereby deteriorating the catalytic performance.

In addition, as a method of not using petroleum as a raw material, studies have been made on production of propylene using methanol, ethanol (especially, bioethanol produced from plants as raw materials), and dimethyl ether as raw materials and using zeolite. Also in this case, there is a problem that the dealumination of zeolite is generated due to the high-temperature steam generated during the reaction and the catalyst performance is deteriorated.

In order to solve the above problems, or for the purpose of further improving the selectivity of a target material, various methods for modifying zeolite with a phosphorus compound have been studied.

For example, Patent Document 1 discloses a catalyst composition for hydrocarbon flow catalytic cracking of fine spherical particles composed of _{5 to} 20 wt% of P ₂ O ₅ , 10 to 50 wt% of pentasil-type zeolite, and 30 to 85 wt% of porous inorganic oxide And a manufacturing method thereof.

Patent Document 2 discloses a fluidized bed reaction catalyst comprising pentacyl zeolite, at least 5 wt% of P ₂ O ₅ and at least 1 wt% of F ₂ O ₃ and having an average particle size of 20 to 200 μm, Method is disclosed.

Patent Document 3 discloses a catalyst made of a substantially inert matrix material of ZSM-5 and / or ZSM-11, which is used in a method for producing light olefins and aromatic compounds from C ₄ ⁺ naphtha hydrocarbons, .

Patent Document 1: Japanese Patent Application Laid-Open No. 2007-244964 Patent Document 2: Japanese Patent Publication No. 2009-500153 Patent Document 3: Japanese Patent Publication No. 2003-504500

However, the inventors of the present invention have found that, by using a catalyst prepared by further testing the examples of the above Patent Documents 1 to 3, corrosion test of a stainless steel commonly used in industrial equipment is carried out under an atmosphere in which high temperature steam presumed as a catalyst regenerator or reactor is present It was found that significant corrosion of the stainless steel occurred. This becomes a major drawback when using industrial catalysts.

SUMMARY OF THE INVENTION In view of the above circumstances, it is an object of the present invention to provide a silica formed body which is less prone to dealumination of zeolite even in a high temperature water vapor atmosphere and which is less susceptible to corrosion of stainless steel used in industrial equipment, And a method thereof.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a silica shaped body containing phosphorus element, zeolite, and silica and produced by a specific method and whose phosphorus content is adjusted to a specific range can solve the above- And have completed the present invention.

That is, the present invention is as follows.

[1] A process for producing a raw material mixture, comprising the steps of: preparing a raw material mixture containing silica and zeolite;

A step of drying the raw material mixture to obtain a dried product,

A method for producing a silica compact having a step of calcining the dried body,

The content of the phosphorus element in the silica shaped body may be adjusted by adding the phosphoric acid and / or the phosphate to the raw material mixture, or by contacting the zeolite and / or the dried body with the phosphoric acid and / or the phosphate solution, By mass based on the mass of the whole.

[2] In the step of bringing the phosphoric acid and / or the phosphate solution into contact with the zeolite and / or the dried product, the amount of the phosphoric acid and / or the phosphate solution is adjusted such that the zeolite and / (1).

[3] The method for producing a silica shaped body according to [1] or [2], further comprising a step of contacting the zeolite with a phosphoric acid and / or a phosphate solution followed by pulverizing the zeolite.

[4] The method for producing a silica shaped body according to any one of [1] to [3], wherein the raw material of the phosphorus element is a phosphate.

[5] The method for producing a silica shaped body according to any one of [1] to [4], wherein the content of the phosphorus element in the silica compact is 0.01 to 0.5 mass% with respect to the mass of the entire silica compact.

[6] The method for producing a silica shaped body according to any one of [1] to [5], wherein the zeolite is of MFI type and SiO ₂ / Al ₂ O ₃ = 20 or more.

[7] The method for producing a silica shaped body according to any one of [1] to [6], further comprising the step of firing the dried body and then contacting the obtained fired body with an acidic liquid.

[8] The method for producing a silica shaped body according to any one of [1] to [7], wherein the silica shaped body substantially contains no aluminum element.

[9] A process for producing propylene,

A process for producing a silica molded article according to any one of the above-mentioned [1] to [8], wherein the obtained silica molded article and a hydrocarbon raw material containing at least one selected from the group consisting of ethylene, ethanol, methanol, In the presence of water vapor.

[10] A process for producing propylene as described in [9] above, wherein the reaction is carried out using a fluidized bed reactor.

[11] The process for producing propylene according to [9] or [10], wherein the WHSV is 0.1 to 1.0 h ^-1 .

[12] The production method of propylene according to any one of [9] to [11], wherein the hydrocarbon raw material contains ethylene in a proportion of 50 mass% or more.

[13] A silica shaped body produced by the production method according to any one of [1] to [8] above.

[14] The silica shaped body according to [13], wherein the corrosion index of the stainless steel is 10000 or less.

[15] A catalyst comprising the silica compact as described in [13] or [14]

A catalyst for producing propylene by contacting a hydrocarbon raw material containing at least one selected from the group consisting of ethylene, ethanol, methanol and dimethyl ether in the presence of steam.

The silica compact obtained by the production method of the present invention is difficult to deal with in the high temperature steam atmosphere, and the corrosion of the stainless steel is small. Therefore, it is preferable as a catalyst for the reaction of producing propylene from a hydrocarbon raw material containing at least one selected from the group consisting of ethylene, ethanol, methanol and dimethyl ether in the presence of steam. It is also suitable as a fluidized bed reaction catalyst because it has excellent properties (good shape, sufficient abrasion resistance) as a fluidized bed reaction catalyst.

1 is an electron micrograph (magnification: 150 times) of the silica compact of Example 1. Fig.
2 is an electron micrograph (magnification: 150 times) of the silica compact of Example 2. Fig.
3 is an electron micrograph (magnification: 150 times) of the silica shaped article of Example 16. Fig.
4 is an electron micrograph (magnification: 150) of the silica compact of Comparative Example 3;
5 is a microscopic photograph (magnification: 120 times) of the test piece after the corrosion test of Example 2. Fig.
6 is a microscopic photograph (magnification: 120 times) of a test piece after the corrosion test of Comparative Example 1. Fig.
7 is a microscopic photograph (magnification: 120 times) of the test piece after the corrosion test of Comparative Example 2. Fig.
Fig. 8 shows changes in the ethylene conversion rate with time in the fluidized phase reaction using the silica compact obtained in Example 1 and Comparative Example 4. Fig.
9 shows the ³¹ solid P-NMR spectrum of the silica compact of Example 1. Fig.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as " present embodiment ") will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

In the present specification, " silica " refers to silica used as a carrier of a silica compact, and does not mean silica constituting zeolite and clay minerals, unless otherwise specified. Likewise, " alumina " refers to alumina used as a carrier for a silica compact, and does not mean alumina constituting zeolite and clay minerals unless specifically mentioned.

In the method for producing a silica compact according to the present embodiment,

A step of preparing a raw material mixture containing silica and zeolite,

A step of drying the raw material mixture to obtain a dried product,

A method for producing a silica compact having a step of calcining the dried body,

The content of the phosphorus element in the silica shaped body may be adjusted by adding the phosphoric acid and / or the phosphate to the raw material mixture, or by contacting the zeolite and / or the dried body with the phosphoric acid and / or the phosphate solution, By mass based on the mass of the whole composition.

[Silica molded article]

The silica compact obtained by the method for producing a silica compact in this embodiment will be explained.

The silica formed body in the present embodiment contains phosphorus element, zeolite and silica. When the silica molded body is used as a catalyst for a reaction for producing propylene from a hydrocarbon raw material containing at least one kind selected from the group consisting of ethylene, ethanol, methanol and dimethyl ether (hereinafter simply referred to as "propylene production reaction"), As a preferable zeolite to be included in the silica compact, there is a zeolite having a three-dimensional pore structure. Examples of the zeolite having such a three-dimensional pore structure include ZSM-5, silicalite and TS-1 in the MFI type and chabazite, ALPO-34 and SAPO-34 in the CHA type. have. Among them, the MFI type having an intermediate pore diameter of about 0.51 to 0.56 nm is preferable. Among them, ZSM-5 is particularly preferable because it has a high heat resistance and characteristic catalytic activity due to shape selectivity and strong acidity desirable.

Here, " MFI " and " CHA " are codes in which zeolite determined by the International Zeolite Association (IZA) is classified according to structure.

The SiO ₂ / Al ₂ O ₃ (molar ratio) of the zeolite is preferably 20 or more, more preferably 20 to 10000, still more preferably 20 to 1000, still more preferably 20 to 500 , And particularly preferably in the range of 200 to 500. < RTI ID = 0.0 > When SiO ₂ / Al ₂ O ₃ (molar ratio) is less than 20, since aluminum in the lattice which is the active point of the zeolite is excessively large, the activity deterioration due to caking tends to accelerate during the propylene production reaction.

SiO ₂ / Al ₂ O ₃ (molar ratio) of the zeolite is relatively high, and when it is used as a catalyst for the propylene production reaction, the yield of propylene tends to be high, which is preferable. In addition, production of propane, a by-product, tends to decrease. This is advantageous industrially because it has the advantage of reducing the burden of the purification process of separating propane and propane having a boiling point. Zeolites not containing Al ₂ O ₃ or zeolites containing trace amounts are called "silicalite" and have little or no acid center due to aluminum. Depending on the use of the silica molded body, silicalite is preferable to silica having a smaller SiO ₂ / Al ₂ O ₃ (molar ratio), and a typical example thereof is a case where it is used as a catalyst for producing caprolactam. On the other hand, in the propylene production reaction, the lower the content of aluminum, the higher the propylene selectivity is, but the lower the activity is, the higher the upper limit of SiO ₂ / Al ₂ O ₃ is preferably about 10,000. As described above, SiO ₂ / Al ₂ O ₃ can be set to an appropriate value in accordance with the use of the silica compact, etc., and thus the upper limit value is not uniformly present.

Zeolites also include metallosilicates of the structure in which the skeletal aluminum atom is replaced with another substitutable metal atom such as gallium, iron, boron, titanium, vanadium, etc., in addition to the aluminosilicate such as ZSM-5.

When the zeolite is a metallosilicate, the aluminum atom and the substituted metal element in the zeolite skeleton are substituted with aluminum atoms to give SiO ₂ / Al ₂ O ₃ (molar ratio). For example, when the zeolite is a silico-aluminate elderly salts, such as SAPO-34, AlO _4, and PO ₄ because a portion of the skeletal Si atoms which is substituted with (Al + P) / Si (atomic ratio) the SiO ₂ / Al ₂ O ₃ (molar ratio).

The degree of crystallization of the zeolite tends to be less likely to cause dealumination in a high temperature steam atmosphere, so that it is preferable that the degree of crystallization is high. The crystallinity of zeolite can be measured by powder X-ray diffractometry. "High degree of crystallinity" means that the diffraction intensity is strong when the diffraction angle is measured in the range of 5 to 50 degrees by a conventional method. In general, when the crystal form of zeolite is a crystal having a definite edge such as a hexagonal plate or cubic form rather than spherical crystals, the diffraction intensity tends to be high.

The content of the zeolite contained in the silica compact of the present embodiment is preferably 15 to 65 mass%, and more preferably 30 to 60 mass%, with respect to the mass of the entire silica compact from the viewpoint of obtaining sufficient activity.

When the silica compact is used as a catalyst for propylene production reaction, the zeolite contained in the silica compact is preferably only MFI type zeolite. However, other zeolites such as SAPO-34 (CHA), Y-type (FAU), super stable Y-type (FAU), mordenite (MOR) and BETA (BEA) coexist in a range not adversely affecting the propylene production reaction . The zeolite contained in the silica compact preferably has an MFI type zeolite of 60 mass% or more, more preferably 80 mass% or more based on the entire zeolite.

The silica compact in this embodiment contains silica. It is not essential that the silica in the silica compact be composed of only silica having a pure SiO ₂ composition, but it may be one contained in an inorganic porous carrier containing silica as a main component. The term " inorganic porous carrier containing silica as a main component " means that the inorganic porous carrier contains 60 mass% or more of silica (the component from which the zeolite and phosphorus elements have been removed from the silica compact as a carrier and based on the mass of the entire carrier) , Preferably 80 mass% or more. A larger amount of silica contained in the inorganic porous carrier is preferable because the wear resistance of the silica compact tends to increase. The inorganic porous carrier may contain clay minerals such as kaolin, zirconia, titania, ceria and the like as the remainder other than silica. The content thereof is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 0% by mass, that is, the carrier is composed solely of silica, based on the mass of the whole carrier. Further, when the silica compact is used as an industrial catalyst, the zeolite-only form lacks the catalyst strength and is not generally realistic.

When the silica shaped body in the present embodiment is used as a catalyst for the propylene production reaction, a form substantially containing no aluminum element such as alumina is more preferable. The phrase " substantially not containing an aluminum element " means that the aluminum element is not contained in an amount that adversely affects the physical properties of the silica compact and the propylene yield of the reaction. However, this aluminum element does not mean aluminum contained in the zeolite framework. Concretely, it is preferably less than 5% by mass in terms of alumina. When the silica compact contains an aluminum element in an amount exceeding 5 mass% with respect to the mass of the entire silica compact, the propylene yield of the reaction tends to be lowered, and the smoothness of the particle surface of the silica compact decreases, And when used as a catalyst in a fluidized bed reaction, it tends to be a weak catalyst having poor fluidity.

The content of the carrier contained in the silica compact in the present embodiment is preferably 35 to 85 mass%, and more preferably 40 to 70 mass%, with respect to the mass of the entire silica compact. When the content of the carrier is less than 35 mass%, the abrasion resistance of the silica compact tends to decrease. When the content of the carrier is more than 85 mass%, the content of zeolite as an active ingredient tends to be lowered.

The silica compact in this embodiment contains phosphorus elements. Examples of the phosphorus element include phosphorus polymers (for example, polyphosphoric acid), phosphorus oxides (for example, P ₂ O ₅ ), phosphorus compounds added to aluminum of zeolite, and the like. Further, a plurality of these may be included.

The phosphorus element has an effect of suppressing the dealumination of zeolite when the zeolite contains aluminum and, in some cases, the effect of improving the propylene yield of the propylene production reaction. Particularly, in the case of an application exposed to a high-temperature steam atmosphere, the characteristics of the silica compact are liable to change due to dealumination, so that the effect becomes even more remarkable.

The content of the phosphorus element contained in the silica compact is 0.01 to 1.0 mass%, preferably 0.01 to 0.5 mass%, more preferably 0.01 to 0.3 mass%, and still more preferably 0.05 to 0.8 mass%, based on the mass of the whole silica compact. 0.3% by mass, particularly preferably 0.1 to 0.3% by mass. When the content of the phosphorus element is less than 0.01 mass%, the effect of suppressing dealumination of the zeolite under a high temperature steam atmosphere is small. When the content of phosphorus element exceeds 1.0 mass%, the corrosion of the stainless steel under high temperature steam atmosphere becomes large.

In the present embodiment, the content of the phosphorus element in the silica compact is a value measured using a fluorescent X-ray analyzer. The content of the phosphorus element is measured by a commercially available fluorescent X-ray analyzer under the usual conditions according to the instruction manual. For example, in the case of using "RIX3000" manufactured by Rigaku, the measurement conditions are P -Kα line can be used, and the local voltage can be 50 kV and the local current 50 mA.

In the case of the use of the silica compact in this embodiment in the case of accommodating the stainless steel container in a container made of stainless steel, the corrosion index is preferably 10000 or less, more preferably 8000 or less, from the viewpoint of preserving stainless steel. In the present embodiment, the corrosion index indicating the corrosion resistance of the stainless steel indicates a value measured by the following method.

The silica compact was pulverized to a particle size of 6 to 16 mesh, and 12 g of the particles were charged into a quartz reaction tube together with a test piece (20 mm x 10 mm, thickness: 1 mm) of stainless steel (SUS304). The reaction tube is maintained at 550 ° C for 7 days while flowing gas (80 vol% of water vapor and 20 vol% of nitrogen). The obtained test specimen is observed with a microscope and the corrosion index is determined according to the following equation.

Corrosion index = number of corners (number of cores / cm < 2 >) x average diameter of corners (mu m) x average depth of cores

Here, the number of holes is determined by measuring the number of holes formed by corrosion per 1 cm 2 of the test piece. The average diameter of the hole is measured by measuring the diameter of the hole formed by the corrosion, and the arithmetic average is obtained. The average depth of corrosion is determined by measuring the depth of the hole caused by corrosion from the section obtained by cutting the test piece, and calculating the arithmetic mean.

Here, " corrosion " refers to a phenomenon in which a metal is altered and destroyed by a chemical reaction or an electrical reaction.

SiO ₂ / Al ₂ O ₃ A preferred combination of (molar ratio) and the element content of the of the silica molded product zeolite is, from the viewpoint of the case of the propylene reaction purposes, while having a high catalytic performance, reducing the corrosion resistance, of zeolite SiO ₂ / Al ₂ O ₃ (molar ratio) is 20-1000, the content of an element preferably from 0.05 to 1.0% by weight, more preferably SiO ₂ / Al ₂ O ₃ (molar ratio) the content of 200 to 1000, the element Is 0.05 to 0.3 mass%.

In the present embodiment, phosphoric acid and / or a phosphate (hereinafter also referred to as " phosphorus raw material ") is used as a raw material of the phosphorus element contained in the silica compact. The term " salt " as used herein refers to a compound produced by a neutralization reaction between an acid and a base described in the textbook of Chemical Society Volume 1, volume 39 (June 15, 2006, Kyoritsu Publishing Co., Ltd.), page 1014, ≪ / RTI > It is preferable that the phosphate is water-soluble. "Water-soluble" means having a solubility of 1 g or more per 100 g of water at 0 ° C. to 25 ° C. As a raw material of the phosphorus element, a phosphate is more preferable. The silica shaped body prepared using phosphate has a tendency that the corrosion resistance of the stainless steel is small even though the phosphorus content of the silica shaped body is the same as that prepared using phosphoric acid.

Specific examples of the phosphoric acid include phosphoric acid and pyrophosphoric acid. Specific examples of the phosphate include ammonium phosphate such as ammonium phosphate, ammonium monophosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium hydrogen phosphate , Aluminum hydrogen phosphate, sodium phosphate, potassium phosphate and the like. Among them, a phosphoric acid ammonium salt having a relatively high solubility in water is preferable, and more preferred is at least one selected from the group consisting of ammonium phosphate, ammonium phosphate monobasic ammonium phosphate and monobasic ammonium phosphate monobasic. These may be used alone or in combination of two or more.

When the silica compact of the present embodiment is used as a catalyst for a fluidized phase reaction, it is preferable that the silica compact is spherical particles having an average particle diameter of 20 to 300 mu m. The average particle diameter of the silica compact is more preferably 30 to 100 占 퐉, and still more preferably 40 to 80 占 퐉. Furthermore, from the viewpoint of fluidity, it is preferable that a particle size distribution in which the particle size of 60% or more of the entirety of the silica shaped body particles is within a range of 2 times to 0.2 times the average particle size. The shape of the silica compact is preferably as close as possible to the actual sphere, and the particle surface is preferably smooth. Here, the average particle size and the particle size distribution can be measured by a laser diffraction / scattering particle size distribution meter (manufactured by Microtrac, trade name " MT3000 ").

In addition, in the above-described catalyst use, a high abrasion resistance is preferable from the viewpoint of less loss of the silica compact during the propylene production reaction. The abrasion resistance of the silica compact can be measured by the impact loss described in the following examples. It is preferable that the attraction loss is smaller, and the measured value by the method described in the embodiment is more preferably 1% by mass or less. The silica compact having high abrasion resistance tends to have a high bulk density because it is a structure (solid sphere) in which the inside of the particle is tightly packed. The preferred bulk density of the silica compact is 0.8 to 1.1 g / cc.

[Production method of silica compact]

In the method for producing a silica compact in this embodiment,

(a) preparing a raw material mixture containing silica and zeolite,

(b) drying the raw material mixture to obtain a dried body,

(c) a step of calcining the dried body,

The content of the phosphorus element in the silica shaped body may be adjusted by adding the phosphoric acid and / or the phosphate to the raw material mixture, or by contacting the zeolite and / or the dried body with the phosphoric acid and / or the phosphate solution, By mass based on the mass of the whole.

In the method for producing a silica compact of the present embodiment, the phosphorus raw material may be carried in advance in the zeolite or may be added to the raw material mixture. It may be carried on a dried body. These may be combined.

It is also preferable to further include a step (step (d)) of bringing the sintered body obtained in the step (c) into contact with the acidic liquid.

[Process (a): Process for preparing raw material mixture]

The step (a) is a step of preparing a raw material mixture containing silica and zeolite, and a raw material mixture is prepared by mixing silica raw material and zeolite.

The addition amount of each component is preferably adjusted so that the silica compact contains 15 to 65 mass% of zeolite and 35 to 85 mass% of silica.

When the zeolite is in an aggregated form (a form in which a part of the primary particles of zeolite of about 0.05 to 2 m form each other to form an aggregate of about 5 to 20 mu m), the zeolite is subjected to mechanical and chemical treatment at 0.05 to 3 mu m Or more, and is preferably agglomerated and used. The method of agglomerating the agglomerates is particularly preferable because dry grinding by a mill such as a jet mill is simple. When the zeolite is in the aggregated form, the zeolite is agglomerated and used to improve the surface smoothness and abrasion resistance of the silica shaped body particles.

The cation of the zeolite is not particularly limited and may be NH ₄ ⁺ or H ⁺ . Other elements (for example, Mg, Ca, Sr, Ba, transition metals such as Ti, Zr, V, Nb, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, Au, Y, La, Ce, and other Zn, B, Ga, Sn, and Sb).

In the production method of the present embodiment, it is also preferable that the phosphoric acid and / or the phosphate solution are brought into contact with the zeolite before the zeolite is mixed with the silica raw material so that the phosphoric acid is carried on the zeolite. As the method, it is preferable to adjust the amount of the phosphoric acid and / or the phosphate solution to an amount such that the zeolite retains the powder state.

The so-called impregnation method is a method in which a zeolite is added to a solution containing a phosphorus raw material to form a slurry state once, the solvent is removed by heating it, and the phosphorous material is supported on the zeolite. According to this method, The process becomes troublesome. In addition, since the zeolite after evaporation of the solvent causes adhesion of the inner surface of the apparatus, it is not suitable for industrial continuous production. On the other hand, a method of supporting a phosphorus raw material on a zeolite by contacting a solution containing zeolite and a phosphorus raw material in such a manner that the zeolite maintains the powder state, that is, the zeolite does not form a slurry state, while controlling the amount of the phosphorus- , It is not necessary to evaporate the solvent and zeolite is not adhered to the apparatus, so industrial continuous production becomes very easy. Further, when a phosphorous material is carried so that the zeolite maintains the powder state, the causticity of the obtained silica shaped body tends to be smaller than that in the case where the slurry state is formed.

Concretely, a solution containing a phosphorus ingredient in a range of 0.2 to 0.5 (mass ratio) to the zeolite (hereinafter also referred to as a "citrate solution", but it is not essential that the phosphorus is in a completely dissolved state) Lt; / RTI > More preferably, a quenching solution of 0.2 to 0.4 (mass ratio) based on the zeolite powder mass is added. As the solvent of the phosphorus raw material, water is preferable. As a method for the addition, it is preferable to use a mixer, a blender, a kneader or the like to make the zeolite flow, and spray the quenching solution uniformly on the zeolite. The temperature is preferably 5 to 95 占 폚. It is preferable to mix the quenching solution at a time sufficient for affinity with the zeolite and the stirring strength, and it is usually 0.5 to 48 hours.

In the case of employing ammonium phosphate as a phosphorus raw material, an aqueous ammonium phosphate solution of 0.3 to 25 mass% is prepared so that the amount of ammonium phosphate is 0.1 to 10 g per 100 g of zeolite Is satisfied. In order to reduce the corrosion index to 8000 or less, it is preferable that the amount of ammonium phosphate is carried so that 0.1 to 5.0 g is satisfied with respect to 100 g of zeolite.

In the case of using phosphoric acid as phosphorus raw material, the phosphorus content of the resulting silica shaped article tends to be higher than that of ammonium phosphate, even though it is the same as that of ammonium phosphate. Therefore, when phosphoric acid is used as phosphorus raw material, it is preferable that the amount of phosphoric acid is carried so as to satisfy 0.1 to 2.0 g with respect to 100 g of zeolite.

The zeolite thus obtained is preferably calcined at 400 to 600 占 폚. Since the fired zeolite tends to cause aggregation, it is preferable that the fired zeolite is agglomerated to about 0.05 to 3 mu m when aggregated. The agglomeration method is preferable in that dry grinding by a grinder such as a hammer mill is simple. When the raw material mixture is prepared by using zeolite in an agglomerated state and then dried and calcined, the mechanical strength and abrasion resistance of the resulting silica compact may be insufficient. It is easy to obtain a silica compact having sufficient mechanical strength and abrasion resistance by pulverizing the agglomerated zeolite and performing the subsequent step.

As the silica raw material of the carrier, colloidal silica, water glass (sodium silicate), fumed silica and the like can be used. It is preferable to use colloidal silica because water glass has a large amount of Na as a catalyst poison and that fumed silica is light in volume density and troublesome in handling. Among them, it is particularly preferable to use colloidal silica of NH ₄ stable type having a lower Na content.

When colloidal silica is used as the silica raw material, the silica particle size of the colloidal silica is preferably small, more preferably 4 to 20 nm, and still more preferably 4 to 15 nm. The use of colloidal silica having a small particle diameter tends to improve wear resistance of the silica compact. Here, the silica particle size can be measured by a laser dynamic light scattering method particle size distribution meter (trade name "NanotracUPA", manufactured by Nikkiso Co., Ltd.).

When colloidal silica is selected as the silica raw material, it is preferable that at least one water-soluble compound selected from the group consisting of nitrates, acetates, carbonates, sulfates and chlorides is present in the raw material mixture. Refers to a compound having a solubility of 1 g or more per 100 g of water at 25 占 폚. The water-soluble compound is preferably a nitrate salt, and each of the ammonium salts is also preferable. More preferably, it is ammonium nitrate. A plurality of these water-soluble compounds may be used at the same time. The presence of these water-soluble compounds in the raw material mixture tends to provide a silica compact having excellent abrasion resistance and a dense structure with a small void in the interior thereof, and this silica compact is suitable for use as a catalyst in a fluidized bed reaction (hereinafter, At least one water-soluble compound selected from the group consisting of the above nitrates, acetates, carbonates, sulfates and chlorides is collectively referred to as " molding aid ").

The addition amount of the molding aid is preferably in a range of 0.01 to 5.0, more preferably in a range of 0.03 to 3.0, and still more preferably in a range of 0.05 to 2.0, in terms of a mass ratio (molding assistant / silica) to silica contained in the colloidal silica More preferably in the range of 0.1 to 1.0, and particularly preferably in the range of 0.25 to 0.5. If the mass ratio is less than 0.01, the silica compact tends to be difficult to form a dense structure. If the mass ratio is more than 5.0, drying tendency tends to decrease during drying.

When these molding aids are present, it is preferable to make the raw material mixture acidic with inorganic acids such as nitric acid, hydrochloric acid and sulfuric acid in order to prevent the colloidal silica from destabilizing (gelation), and more preferably, It is acidic.

The pH of the raw material mixture when the inorganic acid is added is preferably 0.01 to 3.0, more preferably 0.1 to 2.0, and still more preferably 0.5 to 1.5. By preventing the gelation of the colloidal silica and drying the colloidal silica while keeping it in the form of a sol, it is easy to obtain a silica compact having a higher abrasion resistance, which is preferable for the use of a catalyst in a fluidized bed reaction.

The solid content concentration of the raw material mixture is preferably adjusted to 20 to 50 mass%. If the solid content concentration is less than 20 mass%, the abrasion resistance of the silica compact tends to be lowered in the catalyst application for the fluidized phase reaction, and if it exceeds 50 mass%, the smoothness of the surface of the silica compact tends to be slightly lower.

The order of addition of each component contained in the raw material mixture is not particularly limited. Preferably, a zeolite with or without phosphorus elements is added, with the silica source being stirred. Then, if necessary, inorganic acid, a molding aid and the like are added. Further, in the case where the zeolite does not contain phosphorus elements, a desired amount of phosphorus source can be added to this raw material mixture.

The raw material mixture prepared as described above is stirred for a sufficient time for mixing the components and stirring strength. The stirring time is usually 0.1 to 48 hours, and the temperature is usually 5 to 95 ° C.

Further, in the production method of the present embodiment, it is not essential that the raw material mixture contains the phosphorus raw material. That is, when the phosphorous raw material is carried on the dried body as described later, the raw material mixture does not necessarily contain the phosphorous raw material.

[Process (b): drying process]

The step (b) is a step of obtaining a dried body by drying the raw material mixture. When a zeolite containing phosphorus elements is used and phosphorus materials are added to the raw material mixture, these components are also contained in the dried body.

The drying method is not particularly limited. For example, when the silica compact is a catalyst for fluidized phase reaction, it is preferable to dry it using a spray dryer (spray dryer). The spraying method of the raw material mixture can be performed by a rotary disk method, an air flow nozzle method, a pressurized air flow nozzle method, a high pressure nozzle method, or the like. A minute droplet of the sprayed raw material mixture is dried by contacting it with gas heated in the drying chamber in a countercurrent or countercurrent flow. The gas inlet temperature is preferably 100 to 400 캜, and more preferably 150 to 300 캜. The gas outlet temperature is preferably 80 to 200 캜, more preferably 90 to 150 캜. Under various other conditions, a catalyst can be adhered to a very small amount in the drying chamber, spray drying can be stably performed for a long time, and conditions for obtaining desired molded particles can be appropriately selected.

In the case where the silica compact is used as a catalyst for a fixed bed reaction, it is preferable to assemble the raw material mixture into a desired shape and dry it using a heating furnace. The assembly method is preferably an extrusion molding, a compression molding, a transmission assembly, and a flow assembly. The drying temperature is preferably 100 to 400 占 폚, and the drying time is preferably 0.5 to 100 hours.

Whether or not the corrosion index of the silica compact is 10000 or less is not determined by the selection of the drying method or the drying conditions and if the type and amount of the phosphorus material are appropriately set in other steps, none. However, by employing spray drying as the drying method, there is a tendency to obtain a silica compact having a small corrosion index (even if the raw materials are the same) in comparison with other drying methods. Fine grains containing zeolite and silica obtained by spray drying tend to have a phosphorus concentration lower than that of the inside of the grains. In the case where the phosphorus concentration of the particle surface is lower than the internal concentration, the phosphorus concentration in the whole particle is the same and the corrosion resistance tends to be suppressed as compared with that in which phosphorus is uniformly distributed.

In the production method of the present embodiment, the phosphoric acid and / or the phosphate solution may be brought into contact with the dried body obtained by the step (b) to carry the phosphorus raw material. As described above, the method of containing the phosphorus element in the silica compact may include a method of preliminarily supporting the phosphorus raw material on the zeolite or a method of adding the phosphorus material to the raw material mixture, but the phosphorus raw material may be added to the dried body obtained in the step (b) There is a tendency that corrosion of the stainless steel under a high temperature steam atmosphere is further reduced. Therefore, it is a preferred embodiment that the dried body obtained through the steps (a) and (b) does not contain the phosphorus material, and then the phosphorus material is carried on the dried body. In addition, two or more kinds of methods may be used, in which a phosphorus raw material is carried on a zeolite, a phosphorus raw material is added to the raw material mixture, and a phosphorus raw material is carried on the dried body.

The method of supporting the phosphorus raw material on the dried body is not particularly limited. However, as in the case of carrying on the zeolite described above, the amount of the phosphorus containing raw phosphorus is controlled so that the dried body remains in the powder state, It is preferable to bring the solution into contact. Thereby, as described above, the catalyst production process becomes simple, and industrial continuous production becomes very easy. When the silica compact is produced in a powder state, the corrosiveness of the silica compact tends to be smaller than that in the case where the slurry is formed.

Specifically, a solution containing phosphorus in a range of 0.2 to 0.5 (mass ratio) relative to the dried body is added. More preferably 0.2 to 0.4 (mass ratio). As the solvent of the solution containing the phosphorus raw material, water is preferable. The method of addition is preferably a method in which the dried body is caused to flow by using a mixer, a blender, a kneader or the like, and the solution is uniformly sprayed on the dried body. The temperature at that time is preferably 10 to 95 占 폚. It is preferable that the solution is further mixed with the drying time and agitation strength sufficiently, usually 0.5 to 48 hours.

In the case of employing ammonium phosphate as a phosphorus raw material to be added to a dried body, an aqueous ammonium phosphate solution of 0.1 to 15 mass% is prepared and the amount of ammonium phosphate is adjusted to 100 g of the dried body It is preferable to adjust it to 0.05 to 5.0 g. In order to reduce the corrosion index to 8000 or less, it is preferable to adjust the corrosion index to 0.05 to 2.5 g with respect to 100 g of the dried body.

When phosphoric acid is used as the phosphorus raw material, the corrosion index tends to be higher even when the phosphorus content in the resulting silica shaped article is the same as that of ammonium phosphate, as compared with the phosphate such as ammonium phosphate. Therefore, when phosphoric acid is used as the phosphorus raw material, it is preferable to adjust the amount of phosphoric acid to be 0.05 to 2.0 g per 100 g of the dried body.

[Process (c): firing process]

The step (c) is a step of baking the dried body obtained in the step (b), and the dried body is sintered to obtain a sintered body.

The firing of the dried body is not particularly limited, but can be carried out using a muffle, a rotary furnace, a tunnel furnace, a tubular furnace, a flow baking furnace, a kiln furnace or the like. It is industrially preferable to use a continuous feed rotary kiln furnace. From the viewpoint of improving the abrasion resistance of the silica shaped body particles, the firing temperature is preferably 400 to 1000 占 폚, more preferably 500 to 850 占 폚. The baking time is preferably 0.1 to 48 hours, more preferably 0.5 to 10 hours. As the firing atmosphere, air, water vapor, nitrogen, helium and the like can be selected. The firing may be carried out under pressure or under reduced pressure. The firing may be repeated.

The firing process promotes the improvement of the wear resistance of the silica compact particles by the formation of phosphorus compounds from the phosphorus raw material and sintering of the silica contained in the carrier.

[Process (d): Acid cleaning process]

The step (d) is a step of bringing the sintered body obtained by firing in the step (c) into contact with an acidic liquid. In the step (d), it is possible to remove surplus phosphorus components from the calcined body obtained in the step (c), and to remove alkali metal components and the like derived from the silica raw material. By passing through this step, the corrosion resistance to stainless steel can be further reduced.

The conditions of the step (d) are not particularly limited. For example, an aqueous solution containing an inorganic acid such as nitric acid, sulfuric acid, hydrochloric acid and the like at a concentration of 0.1 to 3 moles and the fired body are contacted at a temperature of 10 to 95 캜 for 0.1 to 48 hours . This process may be repeated a plurality of times as necessary.

The acid washing process is not an essential process for obtaining a silica compact having a corrosion index of 10,000 or less. It is also possible to obtain a silica compact having a corrosion index of 10000 or less without acid washing, by appropriately setting the kind and amount of phosphorus raw material. In this case, however, the acidic cleaning can adjust the corrosion index to a more preferable value.

On the other hand, by pickling the silica compact having a corrosion index of more than 10,000, the corrosion index may be adjusted to 10000 or less. In this case, it is preferable to conduct acid pickling using a nitric acid aqueous solution having a concentration of 0.1 to 1 mol, at a temperature of 5 to 50 DEG C for 0.5 to 10 hours and a solid content concentration of 5 to 25 mass%. In order to reduce the corrosion index to 8000 or less, it is preferable to conduct acid pickling using a nitric acid aqueous solution having a concentration of 0.1 to 1 mol, under conditions of 15 to 50 DEG C for 1 to 10 hours and a solid content concentration of 5 to 10 mass%.

After pickling, filtration, washing with water, drying, and further calcining at 400 to 800 ° C, if necessary.

It is also preferable to perform the steaming treatment on the silica compact produced as described above. The steaming treatment may be carried out in a usual manner. For example, the gas containing 10 to 90% by volume of steam (the remainder is usually air) and the silica compact are contacted at a temperature of 500 to 1000 占 폚 for 0.1 to 100 hours. The coking at the time of the reaction described above is suppressed by the steaming treatment, and the yield of propylene tends to be improved.

[Production method of propylene]

Next, a step of contacting the silica molded body obtained by the production method of the present embodiment with a hydrocarbon raw material containing at least one selected from the group consisting of ethylene, ethanol, methanol, and dimethyl ether in the presence of steam, The manufacturing method will be described.

The concentration of ethylene in the hydrocarbon raw material (excluding coexisting steam) is preferably 40 to 100 mass%, more preferably 50 to 80 mass%, still more preferably 50 to 70 mass% %to be. When ethanol, methanol, and dimethyl ether are used, it is assumed that they form ethylene by a dehydration reaction, and the ethylene concentration is taken into consideration.

In the production of propylene, the reaction is carried out in the presence of steam in view of suppressing the activation deterioration due to caking during the reaction. The water vapor concentration is preferably 10 to 60 mass% (based on the raw material including both the hydrocarbon raw material and the water vapor), and more preferably 20 to 40 mass%.

The hydrocarbon raw material may be an alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane or nonane, in addition to ethylene, ethanol, methanol or dimethyl ether; Olefins such as propylene, butene, pentene, hexene, heptene, octene and nonene; Aromas such as benzene, toluene and xylene; Dienes such as butadiene, pentadiene, cyclopentadiene, and cyclohexadiene; And acetylenes such as acetylene, methyl acetylene, and the like. It may also contain oxygen-containing compounds such as propanol, t-butyl alcohol, methyl t-butyl ether, and diethyl ether. In addition, hydrogen sulfide, hydrogen, nitrogen, carbon dioxide, carbon monoxide and the like may be contained.

The above-described reaction is preferably carried out by a fluidized bed method using a fluidized bed reactor. The reaction temperature is preferably in the range of 300 to 650 占 폚, more preferably 400 to 600 占 폚. The reaction pressure is preferably in the range of -0.05 to 1.0 MPa gauge pressure, more preferably 0 (atmospheric pressure) to 0.5 MPa gauge pressure.

The feed rate of the hydrocarbon feedstock is preferably from 0.01 to 10 Hr ^-1 , more preferably from 0.1 to 5.0 hr ^-1 , still more preferably from 0.1 to 5 hr ^-1 , in terms of weight hourly space velocity (WHSV) 1.0 hr < ^{-1 &} gt ;. Here, WHSV can be calculated by the amount of ethylene supplied (kg / h) / the amount of molded silica (kg). In the case of using ethanol, methanol and dimethyl ether, it is assumed that ethylene is formed by the dehydration reaction and the amount of ethylene supplied is taken into consideration.

The silica compact used in the above-mentioned reaction is preferably fired at 400 to 700 占 폚 in an oxygen-containing atmosphere in order to remove the coke accumulated during the reaction. The process of removing the coke by combustion is also referred to as " regeneration process ". In the case of the fixed bed reaction, it is preferable that a plurality of reactors are prepared, and the reaction and the regeneration are alternately performed at predetermined intervals. In the case of the fluidized bed reaction, it is preferable that some or all of the silica compact used for the reaction is introduced into the regenerator and regenerated, and then returned to the reactor to carry out the reaction.

The produced propylene-containing reaction product may be recycled to the reactor together with a part of the high boiling point components such as unreacted ethylene or butene after the objective material such as propylene is separated by distillation or the like.

In the case of producing propylene from ethylene and / or ethanol, since it is an equilibrium reaction, the ethylene conversion rate shows the maximum yield of propylene in the vicinity of 70%. Therefore, in order to obtain propylene efficiently, the reaction is preferably carried out in the range of the ethylene conversion rate of 45 to 85%, more preferably in the range of 50 to 80%.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

[Method of measuring various physical properties]

Measurement methods of various physical properties are as follows.

(1) Structure type of zeolite

The X-ray diffraction pattern of the zeolite was measured using a powder diffraction X-ray apparatus (manufactured by Rigaku, trade name " RINT ") and the structure type was identified by referring to the diffraction pattern of a known zeolite. Measurement conditions were set at a Cu cathode, a pulse voltage of 40 kV, a conduction current of 30 mA, and a scan speed of 1 deg / min.

(2) the zeolite SiO ₂ / Al ₂ O ₃ ratio (molar ratio)

A solution prepared by completely dissolving zeolite in a sodium hydroxide solution was prepared. The amounts of Si and Al contained in the solution were measured by an ordinary method using an ICP (Inductively Coupled Plasma) emission spectrometer (manufactured by Rigaku, trade name "JY138"). From the results, SiO ₂ / Al ₂ O ₃ (Molar ratio). The measurement conditions were set at a high frequency power of 1 kw, a plasma gas of 13 L / min, a sheath gas of 0.15 L / min, a nebulizer gas of 0.25 L / min, a Si measurement wavelength of 251.60 nm, and an Al measurement wavelength of 396.152 nm did.

(3) Phosphorus content of the silica compact

The content of the phosphorus element in the silica compact was measured by a conventional method using a fluorescent X-ray analyzer (manufactured by Rigaku, trade name " RIX3000 "). The measurement conditions were P-K? Line, a voltage of 50 kV and a conduction current of 50 mA. Further, the composition of the other silica compact was calculated from the injection amount of each component.

(4) ³¹ solid P-NMR measurement of the silica compact

The mode of the phosphorus element in the silica shaped article was measured by ³¹ solid P-NMR (manufactured by Bruker, trade name " Biospin DSX400 "). The measurement conditions were an aqueous 85% phosphoric acid solution based on probe: 4BLX-1H, frequency: 161.98 MHz, observation width: 451 ppm, pulse width: 45 degrees, integration: 512 times, chemical shift (0 ppm)

(5) Electron microscope image of the silica compact

The electron microscope image measurement of the silica compact was carried out by an ordinary method using an electron microscope (manufactured by Hitachi, Ltd., trade name " S-800 ").

(6) Bulk density of the silica compact

The bulk density of the silica compact was measured by a conventional method using a volume specific gravity meter (model "Z-2504", manufactured by Tsutsui Rikagaku Kikaku Co., Ltd.).

(7) Measurement of abrasion loss (attrition loss) of silica shaped body particles

The abrasion loss, which is an index of the mechanical strength of the silica shaped body particles, was measured by using a separating flow device. A powder separation unit having an inner diameter of 35 mm and a length of 700 mm and an inner diameter of 110 mm and a length of 600 mm and a fine powder separation unit having an orifice having three 0.4 mm holes, Was used. 52.5 g of a silica compact containing 2.5 g of water at room temperature was introduced into a flow dividing device and air containing a substantial amount of vapor pressure was passed through the gas inlet at 5.8 NL / And the mass of the silica shaped body fine powder recovered in the fine powder collecting part in 5 to 20 hours was measured. The abrasion loss was obtained according to the following formula.

Wear loss (mass%) = A / (B-C) x 100

A represents the mass (g) of the fine powder of the silica-shaped body recovered after 5 to 20 hours from the start of measurement, C represents the mass (g) of the fine powder of the silica-formed body recovered after 0 to 5 hours from the start of measurement, (G) of the silica compact used in the test.

(8) Measurement of corrosion index under high temperature steam atmosphere

The silica compact was pressed and pressed by a compression molding machine, and then crushed to a particle size of 6 to 16 mesh. 12 g of the particles were charged into a quartz reaction tube together with a test piece (20 mm x 10 mm, thickness 1 mm) of stainless steel (SUS304). The reaction tube was maintained at 550 DEG C for 7 days while flowing a gas consisting of 80 vol% of water vapor and 20 vol% of nitrogen. The test piece after the test was observed by a microscope and the corrosion index was measured according to the following formula.

Corrosion index = number of corners (number of cores / cm < 2 >) x average diameter of corners (mu m) x average depth of cores

Here, the number of holes was determined by measuring the number of holes formed by corrosion per 1 cm 2 of the test piece. The average corroded hole diameter was determined by measuring the hole diameter of the hole caused by corrosion, and the arithmetic average thereof was obtained. The average corrosion depth was measured by cutting the test piece, measuring the depth of the hole formed by the corrosion from the obtained cross section, and calculating the arithmetic mean.

(9) Production method of propylene

The silica compacts obtained in the following Examples and Comparative Examples were subjected to a steaming treatment under conditions of a partial pressure of water vapor of 0.8 atm and a partial pressure of nitrogen gas of 0.2 atm at 650 DEG C for 24 hours. 25.7 g of the silica compact was charged into a stainless-steel fluidized bed reactor having an inner diameter of 1 inch. Thereafter, a reactor was charged with 9.9 g / hr of ethylene, 0.7 g / hr of hydrogen, 4.9 g / hr of water and 5.3 g / hr of nitrogen, and a reaction temperature of 550 ° C., a gauge pressure of 0.14 MPa, a WHSV of 0.4 hr ^-1 Silica molded article).

However, when the SiO ₂ / Al ₂ O ₃ ratio of the zeolite in the silica compact was 200 (molar ratio) or more, the amount of the silica molded body was appropriately adjusted in the range of WHSV 0.1-0.4 hr ^-1 . The analysis of the reaction product was carried out by gas chromatography (manufactured by Shimadzu Corporation, GC-17A, TCD-FID series connection type) directly connected to the reactor.

The ethylene conversion rate and propylene yield were derived according to the following formula.

(a) ethylene conversion rate = (ethylene concentration in the feed stream at the inlet of the reactor-ethylene concentration in the feed stream at the outlet of the reactor) / ethylene concentration in the feed stream at the inlet of the reactor x 100

(b) Propylene yield = propylene mass produced by reaction / ethylene mass supplied to reactor × 100

The yield of propylene in the case of using ethanol, methanol, and dimethyl ether as raw materials was calculated by taking ethylene as the amount by which ethylene was formed by the dehydration reaction. The yield of the water produced was not used to derive propylene yield.

The conversion rate of ethanol was derived according to the following formula.

(c) Ethanol conversion rate = (concentration of ethanol in the feed stream at the inlet of the reactor - concentration of ethanol in the feed stream at the outlet of the reactor) / concentration of ethanol in the feed stream at the inlet of the reactor × 100

The conversion of methanol was derived according to the following formula.

(d) Methanol conversion rate = (concentration of methanol in the feed stream at the inlet of the reactor-concentration of methanol in the feed stream at the outlet of the reactor) / concentration of methanol in the feed stream at the inlet of the reactor x 100

The conversion of dimethyl ether was derived according to the following formula.

(e) dimethyl ether conversion rate = (dimethyl ether concentration in the feed stream at the inlet of the reactor-dimethyl ether concentration in the feed stream at the outlet of the reactor) / dimethyl ether concentration in the feed stream at the inlet of the reactor x 100

[Preparation method of zeolite]

With respect to the zeolite used in Examples 1, 10, 17, 18, and 25 and Comparative Examples 1 to 4, the wet cake of the homogeneous compound D was prepared so that the SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of the zeolite was 27 The zeolite was subjected to hydrothermal synthesis in the same manner as in Example 3 of JP-A 2-44771 (Japanese Patent Application Laid-open No. 59-54620), except that it was prepared.

The obtained zeolite was sufficiently washed with water and dried at 120 ° C. Thereafter, in order to convert the cation type of the zeolite into H ⁺ , ion exchange was carried out at 25 ° C for 1 hour using a nitric acid aqueous solution of 1 molar concentration, washed again with water and dried at 120 ° C.

The SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of the thus obtained zeolite was 27 as measured by the aforementioned method. The structure type was determined by MFI type zeolite (ZSM-5) as measured by the above-mentioned method. When identifying the structure type, reference is made to the description of Japanese Patent Publication (Kokoku) No. 46-10064 (hereinafter, the same applies unless otherwise specified).

This zeolite was pulverized (coagulated) so as to have an average particle size of 3 탆 by using a jet mill (manufactured by Nippon Nematic Co., Ltd., type: "LJ") because primary particles were agglomerated.

The zeolite used in Examples 2 to 9, 13 to 16, and Comparative Example 5 was prepared by first preparing a zeolite having a SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of 480 (Example 2) and 50 (Example 3, The aluminum sulfate x (x) contained in the solution A was changed to be the compound (Comparative Example 5), 156 (Example 4), 210 (Example 5), 280 (Manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) and water glass contained in liquid B (manufactured by Fuji Chemical Co., Ltd., trade name "sodium silicate No. 3", 29.0 mass% of SiO ₂ , 9.5 mass% of Na ₂ O, The amount was decided. Subsequently, the liquids A and B were mixed at a rate of 5,000 rpm for 30 minutes using a homogenizer, and hydrothermal synthesis was carried out at 160 DEG C for 3 days (stirring speed 600 rpm). Except for the above, zeolite was subjected to hydrothermal synthesis in the same manner as in Example 2 of Japanese Patent Publication No. 61-21985 (Japanese Patent Laid-Open No. 50-5335).

The obtained zeolite was thoroughly washed with water, dried at 120 ° C and then calcined at 550 ° C for 3 hours in an electric furnace in an air atmosphere. Thereafter, to convert the cation type of the calcined zeolite to NH ₄ ⁺ , ion exchange was performed at 25 ° C for 1 hour using a 1 molar ammonium chloride aqueous solution, followed by washing with water and drying at 120 ° C.

The SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of the zeolite thus obtained was measured by the above-mentioned method and was as described above. The structural type was determined by the above-mentioned method, and all the MFI type zeolite (ZSM-5) was identified.

The zeolite used in Example 12 was synthesized as follows. 970 g of colloidal silica (trade name "Snowex 30", trade name "silica content 31% by mass") and 1040 mass% (Wako Junyaku Co., Ltd., special grade reagent) and 3.06 g of aluminum sulfate · 14-18 whiskey (Wako Junyaku, a special reagent) were mixed using a homogenizer at 5000 rpm for 30 minutes to obtain a solution. The solution was hydrothermally synthesized in an autoclave at 160 ° C for 190 hours (stirring rate: 600 rpm) to obtain zeolite. Followed by water washing, firing and NH ₄ ⁺ exchange in the same manner as above.

The SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of the obtained zeolite was 1000 as measured by the aforementioned method. The structural type was determined by MFI type zeolite (ZSM-5) as measured by the above-mentioned method.

For the zeolite used in Example 11, a commercially available MFI type silicalite was used (manufactured by Jude Chemie Catalyst, trade name: TZP-9023)). The SiO ₂ / Al ₂ O ₃ ratio (molar ratio) of the zeolite was determined to be 10,000 by the aforementioned method. The structural type was determined by MFI type zeolite (ZSM-5) as measured by the above-mentioned method.

[Example 1]

The raw material mixture was prepared as follows (step (a)).

(SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 1) was added to 2000 g of colloidal silica (trade name "Nalco2326", product of Nalco Corporation, silica particle diameter 5 nm, silica content 15 mass% 27) were added. 40 g of a 61% by mass aqueous nitric acid solution (a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to adjust the pH to 1.0, and then 100 g of ammonium nitrate (a special reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added as a molding aid. This raw material mixture was stirred at 25 占 폚 for 2 hours.

The raw material mixture was spray-dried using a spray dryer (manufactured by Okahara Co., Ltd., type: "OC-16") to obtain a dried product (step (b)). A disk type atomizer was used for spraying, and the hot air inlet temperature was 230 캜 and the outlet temperature was 130 캜.

Carrying of the phosphate to this dried body was carried out as follows.

31 g of ammonium dihydrogenphosphate (manufactured by Wako Pure Chemical Industries, Ltd., a special grade reagent, solubility in 100 g of water: 131 g (15 캜)) was dissolved in pure water to prepare 266 g of a phosphate aqueous solution. 665 g of the above dried material was charged in a powder agitator (a locking mixer manufactured by Aichi Electric Industries Co., Ltd.), and the aqueous phosphate solution was sprayed uniformly at 25 캜 while the powder was flowing. The dried product was not in a slurry state, but maintained in a powdery state. This supporting method corresponds to the phosphorus material carrying method A in Tables 1 to 3, and in the examples described later, all of them were held in a powder state when they were carried by the same method.

The obtained dried body carrying the phosphate was fired at 700 ° C for 1 hour in an air atmosphere using a muffle furnace (step (c)).

Finally, this sintered body was added to a nitric acid aqueous solution having a concentration of 0.1 mol, adjusted to a concentration of 10 mass% slurry, and stirred at 25 占 폚 for 1 hour (step (d)).

Thereafter, the slurry was filtered, washed with water, and dried at 120 DEG C for 12 hours to obtain a silica compact.

The analytical results and reaction results of the obtained silica shaped body are shown in Table 1 and FIG.

Brief Description of the Drawings Fig. 1 shows an electron micrograph (magnification: 150) of the silica compact obtained in Example 1. Fig. In Fig. 1, it can be seen that this silica compact is a spherical particle having a smooth surface.

9 shows a ³¹ solid P-NMR signal of the silica compact obtained in Example 1. Fig. In Fig. 9, it can be seen that most of the phosphorus compounds other than phosphoric acid belonging to the signal of -5 to -45 ppm are present in the phosphorus compound of this silica-formed body with almost no phosphorus attributed to the 0 ppm signal.

[Example 2]

The colloidal silica was changed to 882 g of Nalco's trade name "NalcoDVZSN006" (silica particle diameter 12 nm, silica content 34 mass%, pH = 9), and the zeolite was changed to ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio ) = 480) was changed to 300 g, and the phosphorus raw material was changed to 3.1 g of ammonium phosphate monobasic ammonium phosphate.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 1.

2 is an electron micrograph (magnification: 150 times) of the silica compact obtained in Example 2. Fig. In Fig. 2, it can be seen that this silica compact is a spherical particle having a smooth surface.

5 is a micrograph (magnification: 120 times) of an SUS 304 test piece after the corrosion test using the silica compact of Example 2. Fig. In FIG. 5, it can be seen that the test piece after the test has not been corroded.

[Example 3]

The zeolite was changed to 300 g of ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 50), and the phosphorus raw material was dissolved in ammonium dihydrogen phosphate (Wako Pure Chemical Industries, 22.7 g (0 占 폚)) was changed to 26.7 g, to obtain a silica shaped body.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 1.

[Example 4]

The zeolite was changed to 300 g of ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 156), and ammonium phosphate (a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd., solubility in water of 65 g (25 ° C.) ) Was changed to 7.0 g, a silica compact was produced in the same manner as in Example 1.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 1.

[Example 5]

The zeolite was changed to 300 g of ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 210) to obtain 7.6 g of dihydrogen phosphate sodium hydrosulfite (solubility in 100 g of water: 91 g Was sprayed with 133 g of an aqueous solution obtained by dissolving 100 g of water in purified water in the same manner as in Example 1.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 1.

[Example 6]

The zeolite was changed to 300 g of ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 280), and 3.0 g of potassium dihydrogenphosphate (solubility in water of 100 g of water: 14.8 g , A silica compact was produced in the same manner as in Example 1.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 1.

[Example 7]

The procedure of Example 1 was repeated except that zeolite was changed to 300 g of ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 240) and the amount of ammonium dihydrogenphosphate was changed to 9.0 g, To prepare a molded article.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 1.

[Example 8]

(SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 1) was added to 2000 g of colloidal silica (trade name "Nalco2326", product of Nalco Corporation, silica particle diameter 5 nm, silica content 15 mass% 240) was added. Then, 9.0 g of ammonium dihydrogenphosphate was added. Then, 40 g of a 61 mass% nitric acid aqueous solution was added to adjust the pH to 1.0, and then 100 g of ammonium nitrate was added as a molding aid. This raw material mixture was stirred at 25 占 폚 for 2 hours.

Then, by spray drying, calcining, and acid washing in the same manner as in Example 1 except that phosphate was not carried on the dried body, a silica shaped body was produced. This supporting method corresponds to the phosphorus material carrying method B in Tables 1 to 3.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 1.

[Example 9]

500 g of ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 240) was sprayed with 200 g of an aqueous solution containing 12.8 g of ammonium dihydrogenphosphate, while stirring with a mixing stirrer (DALTON, did. At this time, the zeolite was not in the slurry state, but maintained the powder state. This supporting method corresponds to the phosphorus material carrying method C in Table 1, and in the examples described later, the powder was maintained in all cases when it was carried by the same method.

Followed by firing at 600 ° C for 1 hour. Since this sintered body had agglomerated to an average particle size of about 15 mu m, the pulverization treatment was carried out to a mean particle size of 3 mu m or less using Hammer mill (DALTON, type: AIIW-5).

A raw material mixture was prepared in the same manner as in Example 1, except that 300 g of ZSM-5 containing the phosphorus element subjected to the grinding treatment was used.

Then, by spray drying, calcining, and acid washing in the same manner as in Example 1 except that phosphate was not carried on the dried body, a silica shaped body was produced.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 1. The shape of the silica compact obtained in Example 9 was smooth spherical particles as in Examples 1 and 2.

[Example 10]

122 g of alumina sol (trade name " Alumina sol-100 ", trade name; available from Nissan Chemical Industries, Ltd., alumina content 10% by mass) and kaolin (alumina content: 10 mass%) were added to the raw material mixture, and the colloidal silica was changed to 1430 g of trade name "Nalco2326" Manufactured by Engelhard, trade name " APS-600 ") was added and the amount of ammonium dihydrogenphosphate supported on the dried body was changed to 12.6 g.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 2.

[Example 11]

The procedure of Example 9 was repeated except that the zeolite was changed to MFI type silicalite (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 10000) and the amount of ammonium dihydrogenphosphate was changed to 0.7 g, .

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 2.

[Example 12]

A silica compact was produced in the same manner as in Example 8 except that the zeolite was changed to MFI type silicalite (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 1000) and 1.3 g of ammonium dihydrogenphosphate was changed to 1.3 g did.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 2.

[Example 13]

A silica compact was produced in the same manner as in Example 7 except that 5.8 g of phosphoric acid dihydrogenphosphate was changed to phosphoric acid (5.8 g, manufactured by Wako Pure Chemical Industries, Ltd., a special grade reagent).

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 2.

[Example 14]

An example in which zeolite is supported on ammonium monophosphate by impregnation method is shown.

500 g of an aqueous solution containing 12.8 g of ammonium dihydrogenphosphate was added to 500 g of ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 240). The zeolite formed a slurry, not a powder state. The slurry was transferred to a flask, and dried under reduced pressure at 90 ° C using an evaporator. This supporting method corresponds to the phosphorus material carrying method C * in Table 2. Since this zeolite was attached to the inner surface of the flask vessel, it was troublesome to collect it. This was recovered and fired at 600 ° C for 1 hour. This sintered body agglomerated to an average particle size of 30 탆 or more.

A silica compact was produced in the same manner as in Example 9 except that the coagulated form of ZSM-5 containing phosphorus elements was used as it was.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 2.

[Example 15]

An example in which ammonia phosphate is supported on a dried body by an impregnation method is shown.

A dried product was prepared in the same manner as in Example 1 except that the amount of ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 240) was changed to 300 g. 500 g of an aqueous solution containing 9.0 g of ammonium dihydrogenphosphate was added to 500 g of the dried product. The dried body was not in a powder state, but formed a slurry. The slurry was transferred to a flask, and dried under reduced pressure at 90 ° C using an evaporator. This supporting method corresponds to the phosphorus material carrying method A * in Table 2. Since this dried body was attached to the inner surface of the flask container, it was troublesome to collect it. This was recovered and fired at 700 ° C for 1 hour. The sintered body was pickled to obtain a silica compact.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 2.

[Example 16]

In the same manner as in Example 9, zeolite was loaded with ammonium dihydrogen phosphate so that ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 240) remained in the powder state. This was baked at 600 ° C for 1 hour. This sintered body agglomerated to an average particle size of about 15 μm.

A silica compact was produced in the same manner as in Example 9 except that the coagulated form of ZSM-5 containing phosphorus elements was used as it was.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 2.

3 is an electron micrograph (magnification: 150 times) of the silica compact obtained in Example 16. Fig. 3, it can be seen that the silica molded body of Example 16 contains a large number of non-spherical particles with a rough particle surface as compared with the particles of Example 1 (Fig. 1) and Example 2 (Fig. 2) .

[Example 17]

A silica compact was produced in the same manner as in Example 1 except that 12.5 g of ammonium phosphate monoacetate was used and the sintered body was not pickled.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 2.

[Example 18]

As a zeolite, 50 g of CHA type zeolite SAPO-34 (manufactured by Nippon Catalysts Co., Ltd.) and 250 g of ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 27) were mixed and used. A silica molded body was produced in the same manner as in Example 1 except that the amount was changed to 3.1 g.

The analytical results and reaction results of the obtained silica shaped bodies are shown in Table 2.

[Example 19]

The above-mentioned fluidized-bed reaction was carried out for 52 hours using the silica compact of Example 4, and then the catalyst was calcined at 580 ° C for 1 hour in an oxygen-containing atmosphere, and the catalyst was regenerated by removing the coke. Using this regenerated catalyst, a fluidized bed reaction was again carried out under the reaction conditions of Example 4. The initial ethylene conversion rate (at the third reaction time) of the regenerated catalyst was 85.2%, which was more improved than that of Example 4. The yield of propylene was the same as in Example 4.

[Example 20]

The silica compact prepared in Example 5 was crushed after compression molding to obtain particles having a size of 6 to 16 mesh. 8.56 g of this silica-shaped compact was charged in a stainless steel fixed phase reaction tube. Steaming treatment was carried out under conditions of a partial pressure of water vapor of 0.8 atm and a partial pressure of nitrogen gas of 0.2 atm at 650 DEG C for 24 hours. Thereafter, a reactor was charged with 5.8 g / hr of ethylene, 0.4 g / hr of hydrogen, 2.8 g / hr of water and 3.1 g / hr of nitrogen, and a reaction temperature of 550 ° C., a gauge pressure of 0.14 MPa, a WHSV of 0.7 hr ^-1 Silica molded article). The initial ethylene conversion rate (reaction time 3 hours) was 78.5% and the propylene yield was 30.1% (ethylene conversion rate 70%).

[Example 21]

23.0 g of the silica compact produced in Example 6 was charged into a stainless-steel fluidized bed reactor having an inner diameter of 1 inch. Thereafter, 21.6 g / hr of bioethanol (industrial product) and 6.5 g / hr of nitrogen were passed through the reactor and the reaction was carried out at a reaction temperature of 550 캜, a gauge pressure of 0.14 MPa, and a WHSV of 0.6 hr ^-1 I did. The initial conversion rate of ethanol (the third hour of reaction) was 100%, and it was 100% even at 70 hours. The yield of propylene was 27.0%.

[Example 22]

23.0 g of the silica compact prepared in Example 12 was charged into a stainless-steel fluidized bed reactor having an inner diameter of 1 inch. Thereafter, 21.4 g / hr of methanol (a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 4.7 g / hr of nitrogen were passed through the reactor, and a reaction pressure of 0.14 MPa gauge pressure and a WHSV of 0.4 hr ^-1 ). The initial methanol conversion rate (the third reaction time) was 100%, and the 90% methanol conversion rate was 100%. The yield of propylene at this point was 29.5%.

[Example 23]

The silica compact prepared in Example 12 was crushed after compression molding to obtain particles having a size of 6 to 16 mesh. 8.56 g of this silica-shaped compact was charged in a stainless steel fixed phase reaction tube. Steaming treatment was carried out under conditions of a partial pressure of water vapor of 0.8 atm and a partial pressure of nitrogen gas of 0.2 atm at 650 DEG C for 24 hours. Thereafter, 13.3 g / hr of methanol (a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 3.1 g / hr of nitrogen were passed through the reactor, and a reaction temperature of 550 캜, a gauge pressure of 0.14 MPa, a WHSV of 0.7 hr ^-1 ). The initial methanol conversion rate (at the third reaction time) was 100%, and at the 30th hour, it was 100%. The yield of propylene was 42.0%.

[Example 24]

The silica compact prepared in Example 12 was crushed after compression molding to obtain particles having a size of 6 to 16 mesh. 8.56 g of this silica-shaped compact was charged in a stainless steel fixed phase reaction tube. Steaming treatment was carried out under conditions of a partial pressure of water vapor of 0.8 atm and a partial pressure of nitrogen gas of 0.2 atm at 650 DEG C for 24 hours. Thereafter, 9.5 g / hr of dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.1 g / hr of nitrogen were passed through the reactor and the reaction was carried out at a reaction temperature of 550 캜, a gauge pressure of 0.14 MPa and a WHSV of 0.7 hr ^-1 . The initial rate of dimethyl ether conversion (at the 3 rd hour) was 100%, and at the 30 th hour it was 100%. The yield of propylene was 40.0%.

[Example 25]

Except that 500 g of ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 27) was used and 200 g of an aqueous solution containing 38.7 g of ammonium dihydrogenphosphate was used in place of zeolite The raw material was sprayed (phosphorous material carrying method: C). At this time, the zeolite remained in a powder state. This was subjected to pulverizing treatment after firing in the same manner as in Example 9.

300 g of ZSM-5 containing pulverized phosphorus element and 882 g of colloidal silica (trade name "NalcoDVZSN006", manufactured by Nalco Co., Ltd.) were mixed to prepare a raw material mixture, and moisture was evaporated to form a cake. This cake was extrusion-molded with a diameter of 2 mm and a length of 5 mm using an extruder (manufactured by Fuji Powder Co., Ltd., model: MG-55). This was dried at 120 DEG C for 6 hours to obtain a dried body. The obtained dried body was fired at 700 DEG C for 1 hour to obtain a silica compact. The phosphorus content of this silica compact was 0.8 mass% with respect to the mass of the entire silica compact. The corrosion index of this silica compact was 6,000.

[Comparative Example 1]

A silica compact was produced in the same manner as in Example 1 except that the raw material of phosphorus element was changed to 94 g of ammonium dihydrogenphosphate.

Table 3 shows the analytical results of the obtained silica molded article.

6 is a micrograph (magnification: 120 times) of an SUS304 test piece after the corrosion test using the silica compact of Comparative Example 1. Fig. In FIG. 6, holes (black portions) due to corrosion are formed on the surface of the test piece, and it is found that the silica molded body of Comparative Example 1 has high corrosion resistance.

[Comparative Example 2]

A silica compact was produced in the same manner as in Example 1 except that the raw material of phosphorus was changed to 40 g of phosphoric acid.

Table 3 shows the analytical results of the obtained silica molded article.

7 is a microscopic photograph (magnification: 120 times) of the SUS304 test piece after the corrosion test of Comparative Example 2. Fig. In Fig. 7, the entire surface of the test piece is crushed by corrosion, and the silica compact of Comparative Example 2 is highly corrosive.

[Comparative Example 3]

1781 g of alumina sol (trade name: "alumina sol-100", trade name, manufactured by Nissan Chemical Industries, Ltd., alumina content: 10% by mass) was added to the raw material mixture and the phosphorus raw material Was changed to 94 g of ammonium dihydrogenphosphate, to thereby obtain a silica shaped body.

Table 3 shows the analysis results and the reaction results of the obtained silica shaped bodies.

4 is an electron micrograph (magnification: 150) of the silica compact obtained in Comparative Example 3. Fig. From FIG. 4, it can be seen that the silica compact of Comparative Example 4 is distorted in the shape of the particles, has depressed holes on the surface, and has a shape that is far from the smoothness.

[Comparative Example 4]

A silica compact was produced in the same manner as in Example 1 except that no phosphate was supported on the silica compact.

Table 3 shows the analysis results and the reaction results of the obtained silica shaped bodies.

[Comparative Example 5]

85 g of HY type zeolite (SiO ₂ / Al ₂ O ₃ ratio (molar ratio) = 2.5), H-ZSM-5 (SiO ₂ / Al ₂ O ₃ ratio = 50, , 180 g of alumina sol (trade name "alumina sol-100", trade name of alumina, 10 mass%), 190 g of kaolin (manufactured by Engelhardt, trade name "APS-600" And 145 g of ammonium phosphate (manufactured by Wako Pure Chemical Industries, Ltd., a special grade reagent, and a solubility in water of 100 g of water) of 145 g were prepared. This dried body was calcined at 600 DEG C for 1 hour to obtain a silica compact.

Table 3 shows the analysis results and the reaction results of the obtained silica shaped bodies.

As is evident from the results shown in Tables 1 and 2, the silica shaped bodies of the present embodiment (Examples 1 to 18) are remarkably corroded even in the corrosion test using the stainless steel test piece. In addition, it has a good shape and abrasion resistance as a catalyst for fluidized bed reaction, has a high conversion and yield in propylene production, and has excellent catalytic properties.

Comparing Examples 7, 8 and 9, it was found that when the phosphorus material is carried on the dried body (phosphorus material carrying method A) is the least corrosive, and subsequently the phosphorus raw material is carried on zeolite (phosphorus carrier method C ) Is less corrosive, and the phosphorus material is added to the raw material mixture (phosphorus material loading method B), the corrosion is somewhat high.

The comparison between Example 7 and Example 15 and the comparison between Example 9 and Example 14 show that the zeolite and / or the dried body are kept in a powder state when the phosphorus raw material is supported on the zeolite and / or the dried body (Examples 7 and 9) are less likely to be adhered to the catalyst preparation apparatus, which not only facilitates industrial production, but also reduces corrosiveness.

Further, by comparison between Example 9 and Example 16, it is confirmed that the example (Example 9) in which the phosphorus raw material is supported on the zeolite and then subjected to the subsequent step after the pulverization treatment is the silica molded body having good shape and sufficient abrasion resistance It is easy to obtain.

On the other hand, as can be seen from the results shown in Table 3, when the content of the phosphorus element exceeds 1% by mass, it can be understood that the corrosive action is drastically increased. It is also understood that, in the case where the carrier does not contain silica as the main component and contains alumina as the main component (Comparative Example 3), the shape is poor, the bulk density is low, and the abrasion resistance is low, in addition to the increase in the corrosive action. It is also understood that the yield of propylene in the reaction for producing propylene is also low.

As shown in Fig. 8, it can be seen that the silica molded body containing phosphorus elements (Example 1) has a higher initial activity of the reaction as compared with the silica molded body containing no phosphorus element (Comparative Example 4). That is, it can be seen that by containing the phosphorus element, dealumination due to the steaming treatment (treatment with high temperature steam) performed on the silica compact before the reaction hardly occurs and shows high activity.

This application is based on Japanese Patent Application (2010-262752) filed on November 25, 2010, and filed with the Japanese Patent Office, the contents of which are incorporated herein by reference.

The silica shaped body obtained by the production method of the present invention can be preferably used as a catalyst for producing propylene from a hydrocarbon raw material containing at least one selected from the group consisting of ethylene, ethanol, methanol and dimethyl ether under a high temperature steam atmosphere .

Claims (15)

A step of preparing a raw material mixture containing silica and zeolite,
A step of drying the raw material mixture to obtain a dried product,
A method for producing a silica compact having a step of calcining the dried body,
And adjusting the content of the phosphorus element in the silica compact to be 0.01 to 1.0% by mass with respect to the mass of the entire silica compact by contacting the zeolite or the dried or both with phosphate. The method of producing a silica shaped body according to claim 1, wherein, in the step of contacting the zeolite or the dried body or both of the phosphate with the phosphate, the amount of the phosphate is adjusted to an amount that keeps the zeolite or the dried body or both in a powder state. The method according to claim 1 or 2, further comprising a step of pulverizing the zeolite after the step of contacting the zeolite with phosphate. delete The method for producing a silica shaped body according to Claim 1 or 2, wherein the content of the phosphorus element in the silica compact is 0.01 to 0.5 mass% with respect to the mass of the entire silica compact. _{3. The} method for producing a silica shaped body according to claim 1 or 2, wherein the zeolite has an MFI type and SiO ₂ / Al ₂ O ₃ = 20 (molar ratio) or more. The method of manufacturing a silica shaped body according to any one of claims 1 to 5, further comprising a step of firing the dried body and then contacting the obtained fired body with an acidic liquid. 3. The method of producing a silica shaped body according to claim 1 or 2, wherein the silica compact is substantially free of aluminum element. A process for producing propylene, comprising the steps of: preparing a silica compact by the production method according to any one of claims 1 to 3; and mixing the resulting silica compact with at least one member selected from the group consisting of ethylene, ethanol, methanol and dimethyl ether And contacting the hydrocarbon raw material in the presence of water vapor. The process for producing propylene according to claim 9, wherein the reaction is carried out using a fluidized bed reactor. 10. The process for producing propylene according to claim 9, wherein the WHSV is 0.1 to 1.0 h < ^-1 >. The production method of propylene according to claim 9, wherein the hydrocarbon raw material contains ethylene in a proportion of 50 mass% or more. A silica shaped body produced by the production method according to claim 1 or 2. 14. The silica shaped body according to claim 13, wherein the corrosion index of the stainless steel is not more than 10,000. A catalyst for producing propylene by contacting a hydrocarbon raw material containing at least one member selected from the group consisting of ethylene, ethanol, methanol and dimethyl ether in the presence of steam as the catalyst comprising the silica compact according to claim 13.

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